CN104788344A - Bifunctional fluorescent probe adopting anthracene as matrix, as well as preparation method and application - Google Patents
Bifunctional fluorescent probe adopting anthracene as matrix, as well as preparation method and application Download PDFInfo
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- CN104788344A CN104788344A CN201510181059.XA CN201510181059A CN104788344A CN 104788344 A CN104788344 A CN 104788344A CN 201510181059 A CN201510181059 A CN 201510181059A CN 104788344 A CN104788344 A CN 104788344A
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Abstract
The invention provides a bifunctional fluorescent probe which is provided with the structure of the general formula I and adopts anthracene as the matrix. The preparation method of the bifunctional fluorescent probe comprises the following steps: conducting isocyanic acid esterification or isothiocyanic acid esterification on 9-anthracene methylamine; conducting the nucleophilic addition reaction to obtain the bifunctional fluorescent probe. The bifunctional fluorescent probe has the good fluorescence detection effect on iron ions; moreover, the system composed of the bifunctional fluorescent probe and the iron ions has the selective fluorescence enhanced detection effect on fluorine ions.
Description
Technical field
The present invention relates to a class take anthracene as difunctional fluorescent probe compounds of parent and its production and use, belongs to the detection of field of fine chemical intermediate ion.
Background technology
Ferro element is one of element of human body necessity, and its effect is irreplaceable.It is the cofactor of biological enzyme, plays vital effect for the transmission of oxygen and metabolism.If iron content is abnormal, a lot of disease will be caused, such as: gastrointestinal cancer, hepatitis and senile dementia etc.So the content of iron has very important significance in detection life entity.The method of traditional detection iron ion content has atomic absorption spectrometry, resonance ionization mass spectroscopy isotopic dilution method and chromatography etc.In recent years, investigator's extensive concern (Chem.Rev.2013,113,192-270 were received because fluorescence detection has the advantage such as highly sensitive and quick response; Anal.Chim.acta.2014,812,145-151).
Negatively charged ion is prevalent in life entity, and tool plays a very important role, and wherein fluorion is one of indispensable trace element of human body.Fluorine is the important and required integral part of bone and tooth.Appropriate fluorion can prevent the generation of carious disease effectively, so contain the fluorion of trace at toothpaste.If a large amount of absorption fluorions may cause fluorosis, produce the disease such as osteoporosis and urinary calculus immediately; Severe patient may affect intelligence and the physiological system of children.Daily life tap water all contains the fluorion of trace.So the detection of fluorion is particularly important and crucial.(Chem.Rev.2014,114,5511-5571；Chem.Commun.2009,2809-2829；Chem.Soc.Rev.2010,39,3746-3771)。
Detect the method for fluorion have electrochemical process,
19f-NMR analytical method, uv analysis method and fluorometry.First three methods has certain limitation, such as: apparatus expensive, cannot to detect in real time.And utilize fluorometry to have the advantages such as highly sensitive, in real time detection, ultralow density detection and the interior detection of cell, so utilize Fluorometric assay fluorion to be subject to the favor of investigator in recent years.
At present, the detection utilizing same fluorescent probe to realize iron ion and fluorion respectively rarely has report.Based on pyrene, 6,13-five and the fluorescent probe of benzoquinones, naphthalene, quinoline and benzoglyoxaline can realize fluoroscopic examination (Tetrahedron Lett.2010,51, the 5559-5562 of iron ion and fluorion well; Talanta, 2013,105,152-157; Tetrahedron, 2011,67,7909-7912; Supramol.Chem.2015,27,224-232; Sens.Actuators, B 2013,186,657-665), and have not been reported based on the fluorescent probe with this function of anthracene.Based on the research of anthracene difunctional fluorescent probe, there is certain innovation and value so carry out.
Summary of the invention
The detection iron ion that the object of the invention is to provide a class to have premium properties and fluorion take anthracene as the difunctional fluorescent probe of parent.The described structure taking anthracene as the difunctional fluorescent probe of parent and there is general formula I:
Wherein, X is Sauerstoffatom or sulphur atom.
Be the preparation method of the difunctional fluorescent probe of parent with anthracene described in the present invention provides on the other hand, comprise the following steps:
(1) isocyanation esterification or isothiocyanic acid esterification: 9-anthracene methylamine and triphosgene or thiophosgene are reacted, obtains intermediate 9-anthracene methyl isocyanate or 9-anthracene methylisothiocyanate ester;
(2) addition reaction: intermediate 9-anthracene methyl isocyanate or 9-anthracene methylisothiocyanate ester and ammonia solution are reacted, temperature of reaction is 0 ~ 40 DEG C, and the reaction times is 1 ~ 48 hour, obtains fluorescent probe; Described ammonia solution is the one in the Isosorbide-5-Nitrae-dioxane solution of the methanol solution of ammonia, the ethanolic soln of ammonia, the tetrahydrofuran solution of ammonia or ammonia.
The step of described method (1) in, the preparation method of intermediate 9-anthracene methyl isocyanate, be by 9-anthracene methylamine and triphosgene conveniently isocyanation esterification react and prepare.
The step of described method (1) in, the preparation method of intermediate 9-anthracene methylisothiocyanate ester is joined in the mixed solvent of methylene dichloride and water 9-anthracene methylamine and thiophosgene, adds Fu's acid agent calcium carbonate, in 0 ~ 50 DEG C of reaction 1 ~ 24 hour.Described thiophosgene is 1:1-2:1 with the ratio of the amount of substance of 9-anthracene methylamine; Described calcium carbonate is 2:1-3:1 with the ratio of the amount of substance of 9-anthracene methylamine.The volume ratio of described methylene dichloride and water is 0.5:1-2:1.
Of the present invention take anthracene as the preparation method of the difunctional fluorescent probe of parent, step (2) in, ammonia solution is preferably the tetrahydrofuran solution of ammonia, and concentration is 0.2 – 2mol/L.
Again on the one hand, the present invention also provides above-mentioned take anthracene as the application of fluorescent probe in iron ion and fluorion detect of parent.
Fluorescent probe provided by the invention fast, accurately, in real time, optionally can realize the fluoroscopic examination to iron ion in the mixed solvent of dimethyl sulfoxide (DMSO) and water; Can selectivity be realized detecting fluorion Fluorescence Increasing by the system containing iron ion and fluorescent probe simultaneously.
Compared with prior art, the invention has the advantages that:
(1) the fluorescent probe raw material described in is relatively inexpensive, and synthesis step is relatively simple;
(2) fluorescent probe described in is good to the selectivity of ion detection, and fluorometric titration experimental implementation is simple, and change in fluorescence is sharp; And ion pair fluorescent probe has obvious colour-change under visible light, is easy to visual inspection.
Accompanying drawing explanation
Fig. 1 a is fluorescent probe 1 and Fe under visible ray
3+and F
-colour-change after effect; Wherein,
No. 1 is fluorescent probe 1; No. 2 is fluorescent probe 1 and Fe
3+effect; No. 3 is fluorescent probe 1-Fe
3+system and F
-effect;
Fig. 1 b is fluorescent probe 1 and Fe under ultraviolet lamp-365nm
3+and F
-colour-change after effect; Wherein,
No. 1 is fluorescent probe 1; No. 2 is fluorescent probe 1 and Fe
3+effect; No. 3 is fluorescent probe 1-Fe
3+system and F
-effect;
The Fe of Fig. 2 fluorescent probe 1 and different amount
3+effect fluorescence spectrum spectrogram;
The Fe of Fig. 3 fluorescent probe 2 and different amount
3+effect fluorescence spectrum spectrogram;
Fig. 4 fluorescent probe 1 and different metal ionization fluorescence spectrum spectrogram;
Fig. 5 fluorescent probe 1-Fe
3+the F of system and different amount
-effect fluorescence spectrum spectrogram;
Fig. 6 fluorescent probe 2-Fe
3+from the F of different amount
-effect fluorescence spectrum spectrogram;
Fig. 7 fluorescent probe 1-Fe
3+with different anions effect fluorescence spectrum spectrogram.
Embodiment
The present invention is described in detail below in conjunction with embodiment; but the following examples are only the present invention's preferably embodiment; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Embodiment 1 prepares fluorescent probe 1
(1) synthesis of 9-anthracene methyl isocyanate
Under room temperature, 828mg 9-anthracene methylamine is dissolved in 80mL methylene dichloride, then drips the dichloromethane solution 8mL containing 1.2g triphosgene wherein, stirring at room temperature 1 hour; Drip the dichloromethane solution 8mL containing 808mg triethylamine subsequently, react 24 hours; Adding saturated sodium bicarbonate wherein regulates pH to neutral, separatory, and with dichloromethane extraction water layer, separatory, washing organic layer, dry over magnesium sulfate, obtains intermediate 9-anthracene methyl isocyanate 800mg, yield 85% after revolving steaming.
1H-NMR(400MHz,CDCl
3),8.51(s,1H),8.27(d,2H,J＝8.0Hz),8.06(d,2H,J＝8.0Hz),7.62(t,2H,J＝8.0Hz),7.52(t,2H,J＝8.0Hz),5.36(s,2H,CH
2)；
HRMS:Calcd for[M-NCO]
+,191.0861；Found,191.0852.
(2) synthesis of fluorescent probe 1
9-anthracene methyl isocyanate 800mg obtained in the previous step to be dissolved in the tetrahydrofuran solution of 80mL ammonia (0.7mol/L) room temperature reaction 24 hours, suction filtration, a small amount of tetrahydrofuran (THF) washing leaching cake, obtains 800mg fluorescent probe 1 after filter cake dries, yield 93%.
1H-NMR(400MHz,DMSO-d
6),8.60(s,1H),8.43(d,2H,J＝8.0Hz),8.11(d,2H,J＝8.0Hz),7.56(m,4H),6.42(s,1H),5.42(br,2H),5.18(s,2H)；
13C-NMR(100MHz,DMSO-d
6),158.7,131.8,131.6,129.3,126.7,125.7,125.0,36.7；
HRMS:Calcd for[M+H]
+,251.1184；Found,251.1176.
Embodiment 2 prepares fluorescent probe 2
(1) synthesis of 9-anthracene methylisothiocyanate ester
414mg 9-anthracene methylamine is dissolved in 20mL methylene dichloride, adds 520mg calcium carbonate and 20mL water subsequently, finally add 322mg thiophosgene, room temperature reaction 12 hours.In reaction solution, add saturated sodium bicarbonate solution regulates pH to neutral, dichloromethane extraction, and separatory, washing organic layer, dry over magnesium sulfate, obtains intermediate 9-anthracene methylisothiocyanate ester 380mg, yield 76% after revolving steaming.
1H-NMR(400MHz,CDCl
3),8.54(s,1H),8.24(d,2H,J＝8.0Hz),8.07(d,2H,J＝8.0Hz),7.64(t,2H,J＝8.0Hz),7.54(t,2H,J＝8.0Hz),5.60(s,2H).
(2) synthesis of fluorescent probe 2
9-anthracene methylisothiocyanate ester 260mg obtained in the previous step is dissolved in the tetrahydrofuran solution room temperature of 30mL ammonia (0.7mol/L) and reacts 48 hours, revolve and steam removing reaction solvent, then 160mg fluorescent probe 2 is obtained by column chromatography for separation, yield 58%.
1H-NMR(400MHz,DMSO-d
6),8.65(s,1H),8.42(d,2H,J＝8.0Hz),8.14(d,2H,J＝8.0Hz),7.93(s,1H),7.60(m,4H),6.95(br,2H),5.57(s,2H)；
13C-NMR(100MHz,DMSO-d
6),182.6,131.0,130.0,128.9,127.6,126.5,125.3,124.4,40.5；
HRMS:Calcd for[M+H]
+,267.0956；Found,267.0951.
Fluorescent probe 1 and Fe under embodiment 3. visible ray and 365nm
3+and F
-effect
Accurate weighing 25mg fluorescent probe 1 is dissolved in 10mL dimethyl sulfoxide (DMSO), and getting wherein 1mL, to be dissolved in 99mL volume ratio be that in the dimethyl sulfoxide (DMSO) of 1:1 and the mixing solutions of water, making concentration is 10
-4the test fluid 1 of mol/L.Each accurately measure 3mL test fluid 1 successively in No. 1, No. 2 and No. 3 totally 3 sample bottles, subsequently to adding the dimethyl sulphoxide solution that 30 μ L concentration are the iron trichloride of 0.01mol/L in No. 2 and No. 3 sample bottles respectively, the dimethyl sulphoxide solution of the tetrabutyl ammonium fluoride of concentration 30 μ L concentration 0.01mol/L is added in the most backward No. 3 sample bottles, No. 1, No. 2 and No. 33 sample bottles are rocked evenly, the result shown in Fig. 1 a can be obtained under visible light; The result shown in Fig. 1 b can be obtained under ultraviolet 365nm.
The amount of embodiment 4. iron ion is on the impact of fluorescent probe 1 fluorescent emission
Getting concentration in 10mL embodiment 3 is 10
-4the test fluid 1 of mol/L is dissolved in (volume ratio of dimethylene sulfone and water is 4:5) in the mixing solutions of 90mL dimethyl sulfoxide (DMSO) and water, and making concentration is 10
-5the test fluid 2 of mol/L.Get 3mL test fluid 2 in cuvette at every turn, add the dimethyl sulphoxide solution of the iron trichloride of 0.1 equivalent, 1 equivalent, 10 equivalents, 30 equivalents, 50 equivalents, 100 equivalents and 200 equivalents successively, under the effect of 370nm exciting light, test its fluorescence emission spectrum, obtain the result shown in Fig. 2.As can be seen from the figure along with the increase of iron ion amount, fluorescent emission intensity obviously weakens.
Same method can obtain the amount of iron ion to the result of the impact of fluorescent probe 2 fluorescent emission, as shown in Figure 3.
The impact of embodiment 5. different metal ion pair fluorescent probe 1 fluorescent emission
Get concentration in 3mL embodiment 3 is 10 at every turn
-5the test fluid 2 of mol/L, in cuvette, adds the Fe of 100 equivalents successively
3+, Ca
2+, Cr
3+, Cu
2+, Fe
2+, K
+, Li
+, Mg
2+, Mn
2+, Na
+, Ni
2+and Zn
2+, under the effect of 370nm exciting light, test its fluorescence emission spectrum, obtain the result shown in Fig. 4.As can be seen from the figure, fluorescent probe 1 can Selective recognition iron ion well.
The amount of embodiment 6. fluorion is to fluorescent probe 1-Fe
3+the impact of fluorescent emission of system
Get concentration in 3mL embodiment 3 is 10 at every turn
-5the test fluid 2 of mol/L is in cuvette, first the dimethyl sulphoxide solution of 100 equivalent iron trichlorides is added, then the dimethyl sulphoxide solution of the tetrabutyl ammonium fluoride of 1 equivalent, 5 equivalents, 10 equivalents, 20 equivalents, 50 equivalents, 100 equivalents, 101 equivalents, 102 equivalents, 200 equivalents and 300 equivalents is added successively, test its fluorescence emission spectrum, obtain the result shown in Fig. 5.As can be seen from the figure, along with the increase of fluorion amount, the fluorescence of system significantly strengthens.
Same method can obtain the amount of fluorion to fluorescent probe 2-Fe
3+the fluorescent emission of system affect result, as shown in Figure 6.
Embodiment 7. different anions is to fluorescent probe 1-Fe
3+the impact of fluorescent emission of system
Get concentration in 3mL embodiment 3 is 10 at every turn
-5the test fluid 2 of mol/L, in cuvette, first adds the dimethyl sulphoxide solution of 100 equivalent iron trichlorides, then adds the F of 100 equivalents successively
-, Br
-, Cl
-, H
2pO
4 -, HSO
4 -, CH
3cOO
-, CNS
-, CO
3 2-, HCOO
-and I
-, under the effect of 370nm exciting light, test its fluorescence emission spectrum, obtain the result shown in Fig. 7.As can be seen from the figure, system can Selective recognition fluorion.
Claims (7)
1. a class take anthracene as the difunctional fluorescent probe of parent, it is characterized in that: the structure with general formula I,
Wherein, X is Sauerstoffatom or sulphur atom.
2. according to claim 1 take anthracene as the preparation method of the difunctional fluorescent probe of parent, it is characterized in that comprising the following steps:
(1) isocyanation esterification or isothiocyanic acid esterification: 9-anthracene methylamine and triphosgene or thiophosgene are reacted, obtains intermediate 9-anthracene methyl isocyanate or 9-anthracene methylisothiocyanate ester;
(2) addition reaction: intermediate 9-anthracene methyl isocyanate or 9-anthracene methylisothiocyanate ester and ammonia solution are reacted, temperature of reaction is 0 ~ 40 DEG C, and the reaction times is 1 ~ 48 hour, obtains fluorescent probe; Described ammonia solution is the one in the methyl alcohol of ammonia, ethanol, tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane solution.
3. according to claim 2 take anthracene as the preparation method of the difunctional fluorescent probe of parent, it is characterized in that during step (1), the preparation method of 9-anthracene methylisothiocyanate ester is: 9-anthracene methylamine and thiophosgene are joined in the mixed solvent of methylene dichloride and water, add acid binding agent calcium carbonate, in 0 ~ 50 DEG C of reaction 1 ~ 24 hour.
4. according to claim 3 take anthracene as the preparation method of the difunctional fluorescent probe of parent, it is characterized in that: thiophosgene is 1:1-2:1 with the ratio of the amount of substance of 9-anthracene methylamine; Calcium carbonate is 2:1-3:1 with the ratio of the amount of substance of 9-anthracene methylamine.
5. according to claim 3 take anthracene as the preparation method of the difunctional fluorescent probe of parent, it is characterized in that: the volume ratio of described methylene dichloride and water is 0.5:1-2:1.
6. according to claim 2 take anthracene as the preparation method of the difunctional fluorescent probe of parent, it is characterized in that: step (2) in, ammonia solution is the tetrahydrofuran solution of ammonia, and concentration is 0.2 – 2mol/L.
7. according to claim 1 take anthracene as the application of fluorescent probe in iron ion and fluorion detect of parent.
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Cited By (5)
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| CN105085581A (en) * | 2015-09-02 | 2015-11-25 | 大连理工大学 | Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof |
| CN107699228A (en) * | 2017-09-12 | 2018-02-16 | 上海应用技术大学 | A kind of fluorine ion fluorescence probe of nano silicon load, preparation method and applications |
| CN109666001A (en) * | 2019-02-16 | 2019-04-23 | 安徽华胜医药科技有限公司 | A kind of method that multistep processes prepares Elagolix intermediate |
| JP2020091192A (en) * | 2018-12-05 | 2020-06-11 | 学校法人北里研究所 | Compound and use thereof |
| CN113004886A (en) * | 2019-12-20 | 2021-06-22 | 湖南超亟化学科技有限公司 | Preparation method and application of benzoquinolines ratio type near-infrared fluorescent molecular probe for fluorine ion detection |
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| CN105085581A (en) * | 2015-09-02 | 2015-11-25 | 大连理工大学 | Carboxylate radical bridged binuclear iron-sulfur-cluster fluorescent probe, preparation method and application thereof |
| WO2017036133A1 (en) * | 2015-09-02 | 2017-03-09 | 大连理工大学 | Carboxylate radical bridged binuclear iron-sulfur cluster fluorescent probe, preparation method, and application |
| CN105085581B (en) * | 2015-09-02 | 2017-10-24 | 大连理工大学 | One class carboxylate radical bridged binuclear iron-sulfur cluster fluorescence probe, preparation method and application |
| JP2018516886A (en) * | 2015-09-02 | 2018-06-28 | 大連理工大学 | Carboxylic ion cross-linked dinuclear iron sulfur cluster fluorescent probe, its production method and its use |
| US10352917B2 (en) | 2015-09-02 | 2019-07-16 | Dalian University Of Technology | Carboxylate-bridged binuclear iron-sulfur clusters fluorescent probe, preparation method and application thereof |
| CN107699228A (en) * | 2017-09-12 | 2018-02-16 | 上海应用技术大学 | A kind of fluorine ion fluorescence probe of nano silicon load, preparation method and applications |
| CN107699228B (en) * | 2017-09-12 | 2020-01-31 | 上海应用技术大学 | nanometer silicon dioxide loaded fluorine ion fluorescent probe, preparation method and application thereof |
| JP2020091192A (en) * | 2018-12-05 | 2020-06-11 | 学校法人北里研究所 | Compound and use thereof |
| JP7193842B2 (en) | 2018-12-05 | 2022-12-21 | 学校法人北里研究所 | Compounds and uses thereof |
| CN109666001A (en) * | 2019-02-16 | 2019-04-23 | 安徽华胜医药科技有限公司 | A kind of method that multistep processes prepares Elagolix intermediate |
| CN113004886A (en) * | 2019-12-20 | 2021-06-22 | 湖南超亟化学科技有限公司 | Preparation method and application of benzoquinolines ratio type near-infrared fluorescent molecular probe for fluorine ion detection |
| CN113004886B (en) * | 2019-12-20 | 2022-07-08 | 湖南超亟检测技术有限责任公司 | Preparation method and application of benzoquinolines ratio type near-infrared fluorescent molecular probe for fluorine ion detection |
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